Fluorosulfone compounds

ABSTRACT

The present invention relates to new fluorosulfone compounds. These fluorosulfone compounds have utility in preventing, controlling and extinguishing fire.

CROSS REFERENCE(S) TO RELATED APPLICATION(S)

This application claims the priority benefit of U.S. Provisional Application No. 60/494,720, filed Aug. 11, 2003.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to new fluorosulfone compounds. These fluorosulfone compounds have utility in preventing, controlling and extinguishing fire.

2. Description of Related Art

Numerous agents and methods of fire fighting are known and can be selected for a particular fire, depending upon factors such as its size, location and the type of combustible materials involved. Halogenated hydrocarbon fire fighting agents have traditionally been utilized in flooding applications protecting fixed enclosures (e.g., computer rooms, storage vaults, telecommunications switching gear rooms, libraries, document archives, petroleum pipeline pumping stations, and the like), or in streaming applications requiring rapid extinguishing (e.g., military aircraft, commercial hand-held extinguishers). Such extinguishing agents are not only effective but, unlike water, also function as “clean extinguishing agents,” causing little, if any, damage to the enclosure or its contents.

The most commonly-used halogenated hydrocarbon extinguishing agents have been the bromine-containing compounds bromotrifluoromethane (CF₃Br, Halon™1301) and bromochlorodifluoromethane (CF₂ClBr, Halon™1211). These bromine-containing halocarbons are highly effective in extinguishing fires and can be dispensed either from portable streaming equipment or from an automatic room flooding system activated either manually or by some method of fire detection. However, these compounds have been linked to ozone depletion. The Montreal Protocol and its attendant amendments have mandated that Halon™1211 and 1301 production be discontinued.

Thus, there is a need in this field for substitutes or replacements for the commonly-used, bromine-containing fire extinguishing agents. Such substitutes should have a low ozone depletion potential; should have the ability to extinguish, control, and prevent fires, e.g., Class A (trash, wood, or paper), Class B (flammable liquids or greases), and/or Class C (electrical equipment) fires; and should be “clean extinguishing agents,” i.e., be electrically non-conducting, volatile or gaseous, and leave no residue upon use. Preferably, substitutes will also be low in toxicity, not form flammable mixtures in air, have acceptable thermal and chemical stability for use in extinguishing applications, and have short atmospheric lifetimes and low global warming potentials.

BRIEF SUMMARY OF THE INVENTION

The aforementioned objectives of substitutes or replacements for the commonly-used, bromine-containing fire extinguishing agents are met by the present invention which comprises new fluorosulfones having utility in fighting fire.

DETAILED DESCRIPTION OF THE INVENTION

Fluorosulfones of the present invention include trifluoromethyl sulfones, pentafluoroethyl sulfones, and heptafluoroisopropyl sulfones represented by the formula R_(F)SO₂C_(a)H_(b)X_(c)F_(d), wherein: RF is selected from the group consisting of CF₃, C₂F₅, and CF(CF₃)₂; X is selected from the group consisting of Cl, Br and 1, preferably Br; a is 1, 2 or 3, preferably 1 or 2; b is 0 or 1; c is 0, 1 or 2, preferably 1; d is O or an integer from 1 to 5; b+c+d=2a+1; and b+c≧1; with the proviso that CF₃SO₂CCl₂CF₃ is not included.

Representative trifluoromethyl sulfones include CF₃SO₂CHF₂, CF₃SO₂CClF₂, CF₃SO₂CBrF₂, CF₃SO₂CF₂, CF₃SO₂CHClCF₃, CF₃SO₂CHFCBrF₂, CF₃SO₂CClFCClF₂, CF₃SO₂CBrFCBrF₂, CF₃SO₂CFICF₃, and CF₃SO₂CF₂CF₂I.

These trifluoromethylsulfones may be prepared by reaction of a fluoro(halo)(hydro)sulfonyl fluoride with a source of CF₃ anion such as CF₃Si(CH₃)₃ in the presence of fluoride ion as described by Patel et al. in Inorganic Chemistry, (1992), v. 31, p. 2537.

For example, CF₃SO₂CHF₂ may be prepared by reacting FSO₂CHF₂ with CF₃Si(CH₃)₃ in the presence of fluoride, CF₃SO₂CClF₂ may be prepared by reacting FSO₂CClF₂ with CF₃Si(CH₃)₃ in the presence of fluoride, CF₃SO₂CBrF₂ may be prepared by reacting FSO₂CBrF₂with CF₃Si(CH₃)₃ in the presence of fluoride, CF₃SO₂CF₂I may be prepared by reacting FSO₂CF₂I with CF₃Si(CH₃)₃ in the presence of fluoride, CF₃SO₂CHClCF₃ may be prepared by reacting FSO₂CHClCF₃ with CF₃Si(CH₃)₃ in the presence of fluoride, CF₃SO₂CHFCBrF₂ may be prepared by reacting FSO₂CHFCBrF₂ with CF₃Si(CH₃)₃ in the presence of fluoride, CF₃SO₂CClFCClF₂ may be prepared by reacting FSO₂CClFCClF₂ with CF₃Si(CH₃)₃ in the presence of fluoride, CF₃SO₂CBrFCBrF₂ may be prepared by reacting FSO₂CBrFCBrF₂ with CF₃Si(CH₃)₃ in the presence of fluoride, CF₃SO₂CFICF₃ may be prepared by reacting FSO₂CFICF₃ with CF₃Si(CH₃)₃ in the presence of fluoride, and CF₃SO₂CF₂CF₂I may be prepared by reacting FSO₂CF₂CF₂I with CF₃Si(CH₃)₃ in the presence of fluoride.

Representative pentafluoroethyl sulfones include CF₃CF₂SO₂CHF₂, CF₃CF₂SO₂CClF₂, CF₃CF₂SO₂CBrF₂, CF₃CF₂SO₂CF₂I, CF₃CF₂SO₂CHClCF₃, CF₃CF₂SO₂CHFCBrF₂, CF₃CF₂SO₂CCl₂CF₃, CF₃CF₂SO₂CClFCClF₂, CF₃CF₂SO₂CBrFCBrF₂, CF₃CF₂SO₂CFICF₃, and CF₃CF₂SO₂CF₂CF₂I.

These pentafluoroethyl sulfones may be prepared by reaction of an appropriate sulfonyl fluoride with tetrafluoroethylene in the presence of fluoride in an anhydrous polar solvent by a process similar to that described by Temple in Journal of Organic Chemistry, (1968), v.33, p.344, and French patent application no. 1,555,130.

For example, CF₃CF₂SO₂CHF₂ may be prepared by reacting FSO₂CHF₂ with tetrafluoroethylene in the presence of fluoride, CF₃CF₂SO₂CClF₂ may be prepared by reacting FSO₂CClF₂ with tetrafluoroethylene in the presence of fluoride, CF₃CF₂SO₂CBrF₂ may be prepared by reacting FSO₂CBrF₂ with tetrafluoroethylene in the presence of fluoride, CF₃CF₂SO₂CF₂I may be prepared by reacting FSO₂CF₂I with tetrafluoroethylene in the presence of fluoride, CF₃CF₂SO₂CHClCF₃ may be prepared by reacting FSO₂CHClCF₃ with tetrafluoroethylene in the presence of fluoride, CF₃CF₂SO₂CHFCBrF₂ may be prepared by reacting FSO₂CHFCBrF₂ with tetrafluoroethylene in the presence of fluoride, CF₃CF₂SO₂CCl₂CF₃ may be prepared by reacting FSO₂CCl₂CF₃ with tetrafluoroethylene in the presence of fluoride, CF₃CF₂SO₂CClFCClF₂ may be prepared by reacting FSO₂CClFCClF₂ with tetrafluoroethylene in the presence of fluoride, CF₃CF₂SO₂CBrFCBrF₂ may be prepared by reacting FSO₂CBrFCBrF₂ with tetrafluoroethylene in the presence of fluoride, CF₃CF₂SO₂CFICF₃ may be prepared by reacting FSO₂CFICF₃ with tetrafluoroethylene in the presence of fluoride, and CF₃CF₂SO₂CF₂CF₂I may be prepared by reacting FSO₂CF₂CF₂I with tetrafluoroethylene in the presence of fluoride.

Representative heptafluoroisopropyl sulfones include (CF₃)₂CFSO₂CHF₂, (CF₃)₂CFSO₂CClF₂, (CF₃)₂CFSO₂CBrF₂, (CF₃)₂CFSO₂CF₂₁, (CF₃)₂CFSO₂CHClCF₃, (CF₃)₂CFSO₂CHFCBrF₂, (CF₃)₂CFSO₂CCl₂CF₃, (CF₃)₂CFSO₂CClFCClF₂, (CF₃)₂CFSO₂CBrFCBrF₂, (CF₃)₂CFSO₂CFICF₃ and (CF₃)₂CFSO₂CF₂CF₂I.

These heptafluoroisopropyl sulfones may be prepared by reaction of an appropriate sulfonyl fluoride with hexafluoropropene in the presence of fluoride in an anhydrous polar solvent by a process similar to that described by Temple in Journal of Organic Chemistry, (1968), v.33, p.344, and French patent application no. 1,555,130.

For example, (CF₃)₂CFSO₂CHF₂ may be prepared by reacting FSO₂CHF₂ with hexafluoropropene in the presence of fluoride, (CF₃)₂CFSO₂CClF₂ may be prepared by reacting FSO₂CClF₂ with hexafluoropropene in the presence of fluoride, (CF₃)₂CFSO₂CBrF₂ may be prepared by reacting FSO₂CBrF₂ with hexafluoropropene in the presence of fluoride, (CF₃)₂CFSO₂CF₂I may be prepared by reacting FSO₂CF₂I with hexafluoropropene in the presence of fluoride, (CF₃)₂CFSO₂CHClCF₃ may be prepared by reacting FSO₂CHClCF₃ with hexafluoropropene in the presence of fluoride, (CF₃)₂CFSO₂CHFCBrF₂ may be prepared by reacting FSO₂CHFCBrF₂ with hexafluoropropene in the presence of fluoride, (CF₃)₂CFSO₂CCl₂CF₃ may be prepared by reacting FSO₂CCl₂CF₃ with hexafluoropropene in the presence of fluoride, (CF₃)₂CFSO₂CClFCClF₂ may be prepared by reacting FSO₂CClFCClF₂ with hexafluoropropene in the presence of fluoride, (CF₃)₂CFSO₂CBrFCBrF₂ may be prepared by reacting FSO₂CBrFCBrF₂ with hexafluoropropene in the presence of fluoride, (CF₃)₂CFSO₂CFICF₃ may be prepared by reacting FSO₂CFICF₃ with hexafluoropropene in the presence of fluoride, and (CF₃)₂CFSO₂CF₂CF₂I may be prepared by reacting FSO₂CF₂CF₂I with hexafluoropropene in the presence of fluoride.

The present invention further includes perfluorosulfones CF₃SO₂CF₂CF₂CF₃, CF₃SO₂C(CF₃)₃, CF₃SO₂CF₂CF(CF₃)₂, CF₃SO₂CF(CF₃)CF₂CF₃, CF₃CF₂SO₂CF₂CF₂CF₃, CF₃CF₂SO₂CF(CF₃)₂, CF₃CF₂CF₂SO₂CF(CF₃)₂, and (CF₃)₂CFSO₂CF(CF₃)₂.

Perfluorosulfones CF₃CF₂SO₂CF₂CF₂CF₃, CF₃SO₂CF(CF₃)CF₂CF₃, CF₃SO₂C(CF₃)₃, CF₃CF₂SO₂CF(CF₃)₂, CF₃CF₂CF₂SO₂CF(CF₃)₂ and (CF₃)₂CFSO₂CF(CF₃)₂ may be prepared by reacting an appropriate perfluoroalkyl sulfonyl fluoride with a perfluoroolefin in the presence of fluoride in an anhydrous polar solvent by a process similar to that described by Temple in Journal of Organic Chemistry, (1968), v.33, p.344, and French patent application no. 1,555,130.

For example, CF₃CF₂SO₂CF₂CF₂CF₃ may be prepared by reacting FSO₂CF₂CF₂CF₃ with tetrafluoroethene in the presence of fluoride, CF₃SO₂CF(CF₃)CF₂CF₃ may be prepared by reacting FSO₂CF₃ with perfluoro-2-butene in the presence of fluoride, CF₃SO₂C(CF₃)₃ may be prepared by reacting FSO₂CF₃ with perfluoroisobutylene in the presence of fluoride, CF₃CF₂SO₂CF(CF₃)₂ may be prepared by reacting CF₃CF₂SO₂F with hexafluoropropene in the presence of fluoride, CF₃CF₂CF₂SO₂CF(CF₃)₂ may be prepared by reacting CF₃CF₂CF₂SO₂F with hexafluoropropene in the presence of fluoride, and (CF₃)₂CFSO₂CF(CF₃)₂ may be prepared by reacting SO₂F₂ or FSO₂CF(CF₃)₂ with hexafluoropropene in the presence of fluoride.

Perfluorosulfone CF₃SO₂CF₂CF₂CF₃ may be prepared by the fluorination of known CCl₃SO₂CF₂CF₂CF₃ with HF or SbF₃/SbCl₅ in the liquid phase. Alternatively, CF₃SO₂CF₂CF₂CF₃ may be prepared by direct fluorination of known CH₃SO₂CH₂CH₂CH₃ using the techniques reported by Harmon et al. in Journal of the Chemical Society, Perkin Transaction I, (1979), p.2675.

Perfluorosulfone CF₃SO₂CF₂CF(CF₃)₂ can be made using the techniques disclosed by Haszeldine, et.al. in Journal of the Chemical Society, Perkin Transaction I, (1972), p.2180, beginning with diisobutyl disulfide and trifluoromethyl iodide. The resulting trifluoromethyl isobutylsulfide may then be oxidized to the sulfone as disclosed by Haszeldine in U.S. Pat. No. 3,816,277, and finally perfluorinated according to the methods of Harmon et al. in Journal of the Chemical Society, Perkin Transaction I, (1979), p.2675.

The present invention further includes hydrofluorosulfones CF₃CH₂SO₂CF₂CF₃, CF₃CH₂SO₂CF(CF₃)₂, and CH₃SO₂CF₂CF₃.

These hydrofluorosulfones may be prepared by reacting appropriate sulfonyl fluorides with perfluoroolefins in the presence of fluoride in an anhydrous polar solvent by the process of Temple in Journal of Organic Chemistry, (1968), v.33, p.344, and French patent application no. 1,555,130.

For example, CF₃CH₂SO₂CF₂CF₃ may be prepared by reacting FSO₂CH₂CF₃ with tetrafluoroethene, and CF₃CH₂SO₂CF(CF₃)₂ may be prepared by reacting FSO₂CH₂CF₃ with hexafluoropropene.

Hydrofluorosulfone CH₃SO₂CF₂CF₃ may be prepared by reacting C₂F₅₁ with CH₃SSCH₃ followed by oxidation of the intermediate sulfide using the process described by Haszeldine, et. al. in Journal of the Chemical Society Perkin Trans. I, (1972), p.159.

The present invention further includes halomethyl perfluoroalkyl sulfones CH₂ClSO₂CF₂CF₃, CH₂BrSO₂CF₂CF₃, CH₂ISO₂CF₂CF₃, CH₂ClSO₂CF(CF₃)₂, CH₂BrSO₂CF(CF₃)₂, CH₂ISO₂CF(CF₃)₂, CH₂ClSO₂CF₂CF₂CF₃, CH₂BrSO₂CF₂CF₂CF₃, CH₂ISO₂CF₂CF₂CF₃, CH₂BrCH₂SO₂CF₃, CH₂ClCH₂SO₂C₂F₅ and CH₂BrCH₂SO₂C₂F₅.

These halomethyl perfluoroalkyl sulfones may be prepared by reacting a metallated methyl perfluoroalkyl sulfone with chlorine (Cl₂), bromine (Br₂), or iodine (I₂). The methyl perfluoroalkyl sulfone may be metallated by reaction with tert-butyl lithium or a Grignard reagent such as methyl magnesium bromide in a solvent such as ether, tetrahydrofuran, dimethoxyethane and diglyme free of compounds containing acidic hydrogen atoms (e.g., water).

For example, CH₂XSO₂CF₂CF₃, wherein X is Cl, Br or I, may be prepared by reacting CH₃SO₂CF₂CF₃ with a stoichiometric amount of tert-butyl lithium at −78° C. in anhydrous diethyl ether to form intermediate (Li⁺)(⁻CH₂SO₂CF₂CF₃), which is then promptly reacted in the same reaction vessel with a stoichiometric amount of chlorine, bromine or iodine.

For example, CH₂ClSO₂CF₂CF₃ may be prepared by reacting CH₃SO₂CF₂CF₃ with a stoichiometric amount of tert-butyl lithium at −78° C. in anhydrous diethyl ether to form intermediate (Li⁺)(⁻CH₂SO₂CF₂CF₃) which is then promptly reacted in the same reaction vessel with a stoichiometric amount of chlorine. The iodomethyl compounds may also be prepared by reacting trimethylsilyl iodomethane with tert-butyl lithium followed by trifluoromethanesulfonic anhydride as described by Mahadevan et al. in Tetrahedron Letters, (1994), v.35, p. 6025.

CH₂BrCH₂SO₂CF₃ and CH₂BrCH₂SO₂C₂F₅ may be prepared by reacting the corresponding ethyl perfluoroalkylsulfones with bromine in the presence of a radical initiator or UV light in a solvent such as carbon tetrachloride.

CH₂ClCH₂SO₂C₂F₅ may be prepared by reacting the ethyl perfluoroethyl sulfone with chlorine in the presence of UV light using a process similar to that described by Laping and Hanack in Tetrahedron Letters, 1979, pages 1309 to 1310.

Fluorosulfones of the present invention have utility in fire fighting as fire preventing, controlling and extinguishing agents.

The present fluorosulfones may be utilized alone, in combination with one another, or in combination with a co-fire-fighting agent or propellant selected from known fire fighting agents of the classes hydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons, perfluoroketones, bromoperfluoroketones, perfluoropolyethers, hydrofluoropolyethers, hydrofluoroethers, chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons, hydrobromocarbons, iodofluorocarbons, and hydrobromofluorocarbons. Such co-agents can be chosen to enhance the fire fighting capabilities or modify the physical properties (e.g., modify the rate of introduction by serving as a propellant) of a fire fighting composition for a particular type (or size or location) of fire hazard and can preferably be utilized in ratios (of co-agent to fluorosulfone) such that the resulting composition does not form flammable mixtures in air. Such fire fighting mixtures may contain from about 10-90% by weight of at least one fluorosulfone and from about 90-10% by weight of at least one co-agent.

Of particular utility are azeotropic and azeotrope-like mixtures containing the present fluorosulfones and one or more compounds selected from the group consisting of perfluoroketones, bromoperfluoroketones and hydrofluorocarbons. Such mixtures may provide a fire fighting composition with a lower boiling point than either constituent of the mixture as well as provide a constant ratio of the components of the mixture during discharge.

The present fluorosulfones may be solids, liquids, or gases under ambient conditions, but are preferably utilized for fire preventing, controlling and extinguishing in either the liquid or the gaseous state (or both). Thus, normally solid compounds are preferably utilized after transformation to liquid and/or gas through melting, sublimation, or dissolution in a liquid co-agent. Such transformation can occur upon exposure of the compound to the heat of a fire. Introduction of a fire controlling or extinguishing composition can generally be carried out by releasing the composition into an enclosed area surrounding a fire. Any of the known methods of introduction can be utilized provided that appropriate quantities of the composition are metered into the enclosed area at appropriate intervals. For example, a composition can be introduced by streaming, e.g., using conventional portable (or fixed) fire extinguishing equipment; by misting; or by flooding, e.g., by releasing (using appropriate piping, valves, and controls) the composition into an enclosed area surrounding a fire. The composition can optionally be combined with an inert propellant, e.g., nitrogen, argon, decomposition products of glycidyl azide polymers or carbon dioxide, to increase the rate of discharge of the composition from the streaming or flooding equipment utilized. When the composition is to be introduced by streaming or local application, fluorosulfones having normal boiling points in the range of from about 40° C. to about 130° C. (especially fluorosulfones that are liquid under ambient conditions) are preferably utilized. When the composition is to be introduced by misting, fluorosulfones having boiling points in the range of from about 40° C. to about 110° C. are generally preferred. And, when the composition is to be introduced by flooding, fluorosulfones having boiling points in the range of from about 40° C. to about 80° C. are generally preferred.

Preferably, the extinguishing composition is introduced to a fire or flame in an amount sufficient to extinguish the fire or flame. One skilled in this field will recognize that the amount of extinguishing composition needed to extinguish a particular fire will depend upon the nature and extent of the hazard. When the extinguishing composition is to be introduced by flooding, cup burner test data is useful in determining the amount or concentration of extinguishing composition required to extinguish a particular type and size of fire. The amount of fluorosulfone used to control or extinguish fire is generally an average resulting concentration of between about 1 and about 10 percent by gas volume of fluorosulfone.

The present fluorosulfones are also useful for preventing a combustible material from igniting. The present fluorosulfones thus also have utility in preventing fires or deflagration in an air-containing, enclosed area that contains combustible materials of the self-sustaining or non-self-sustaining type. Such a utility involves a process comprising the step of introducing into an air-containing, enclosed area a non-flammable fire preventing composition that is essentially gaseous that comprises at least one present fluorosulfone, the composition being introduced and maintained in an amount sufficient to prevent combustion of combustible materials in the enclosed area.

For fire prevention, fluorosulfones (and any co-agent(s) utilized) can be chosen so as to provide a composition that is essentially gaseous under use conditions. Preferred compound(s) have boiling points in the range of from about 40° C. to about 130° C. The fluorosulfone composition is introduced and maintained in an amount sufficient to prevent combustion of combustible materials in the enclosed area. The amount varies with the combustibility of the particular flammable materials present in the enclosed area. Combustibility varies according to chemical composition and according to physical properties such as surface area relative to volume, porosity, etc. The present fluorosulfones can be used to eliminate the combustion-sustaining properties of air and to thereby prevent the combustion of flammable materials (e.g., paper, cloth, wood, flammable liquids, and plastic items). The present fluorosulfones can be maintained continuously if a threat of fire is always present or can be introduced into an atmosphere as an emergency measure if a threat of fire or deflagration develops.

EXAMPLES Example 1 Synthesis of CF₃CF₂SO₂CF₂CF₂CF₃

CF₃CF₂SO₂CF₂CF₂CF₃ is prepared by reacting FSO₂CF₂CF₂CF₃ with tetrafluoroethene in the presence of fluoride ion in anhydrous diethyl ether by the method of Temple in Journal of Organic Chemistry, (1968), v.33, p.344, and French patent application no. 1,555,130.

FSO₂CF₂CF₂CF₃ is prepared by the electrochemical fluorination of known FSO₂CH₂CH₂CH₃ by the method of Hollitzer et al. as disclosed in Journal of Fluorine Chemistry, (1987), v.35, no. 2, p.329.

Example 2 Fire Extinguishing Concentration of CF₃CF₂SO₂CF₂CF₂CF₃

The fire extinguishing concentration of CF₃CF₂SO₂CF₂CF₂CF₃, is determined by the NFPA Standard Cup Burner method. This method is described in NFPA 2001-2003, Annex B.

Specifically, an air stream is passed at 40 liters/minute through an outer chimney (8.5 cm. I. D. by 53 cm. tall) from a glass bead distributor at its base. A fuel cup burner (3.1 cm. O.D. and 2.15 cm. I.D.) is positioned within the chimney at 23.5 cm above the top of the bead distributor. The fire extinguishing agent is added to the air stream prior to its entry into the glass bead distributor while the air flow rate is maintained at 40 liters/minute for all tests. The air and agent flow rates are measured using calibrated rotameters.

The test is conducted by adjusting the fuel (n-heptane) level in the reservoir to bring the liquid fuel level in the cup burner just even with the ground glass lip on the burner cup. With the air flow rate maintained at 40 liters/minute, the fuel in the cup burner is ignited. The fire extinguishing agent is added in measured increments until the flame is extinguished.

The fire extinguishing concentration is determined by thermal conductivity gas chromatography. A sample of the air is taken from the chimney in a gas-tight syringe and injected into the gas chromatograph that has been calibrated for the agent. TABLE 1 FIRE EXTINGUISHING CONCENTRATION FIRE EXTINGUISHING AGENT (volume % in air) EXAMPLE CF₃CF₂SO₂CF₂CF₂CF₃ 6 COMPARATIVE CF₃CHFCF₃ (HFC-227ea) 7.3 CF₃CHFCHF₂ (HFC-236ea) 10.2 CF₃CF₂CH₂Cl (HCFC-235cb) 6.2 CF₄ 20.5 C₂F₆ 8.7 CF₃Br (Halon-1301) 4.2 CF₂ClBr (Halon 1211) 6.2 CHF₂Cl 13.6 

1. A compound represented by the formula R_(F)SO₂C_(a)H_(b)X_(c)F_(d), wherein: R_(F) is selected from the group consisting of CF₃, C₂F₅, and CF(CF₃)₂; X is selected from the group consisting of Cl, Br and I; a is 1, 2 or 3; b is 0 or 1; c is 0, 1 or 2; d is 0 or an integer from 1 to 5; b+c+d=2a+1; and b+c≧1; with the proviso that CF₃SO₂CCl₂CF₃ is not included.
 2. A compound of claim 1 wherein X is Br; a is 1 or 2; and c is
 1. 3. A compound of claim 1 which is selected from the group consisting of: CHF₂SO₂CF₂CF₃, CHF₂SO₂CF(CF₃)₂, CF₃SO₂CHF₂, CF₃SO₂CClF₂, CF₃SO₂CBrF₂, CF₃SO₂CF₂I, CF₃SO₂CHClCF₃, CF₃SO₂CHFCBrF₂, CF₃SO₂CClFCClF₂, CF₃SO₂CBrFCBrF₂, CF₃SO₂CFICF₃, CF₃SO₂CF₂CF₂₁, CF₃CF₂SO₂CHF₂, CF₃CF₂SO₂CClF₂, CF₃CF₂SO₂CBrF₂, CF₃CF₂SO₂CF₂₁, CF₃CF₂SO₂CHClCF₃, CF₃CF₂SO₂CHFCBrF₂, CF₃CF₂SO₂CCl₂CF₃, CF₃CF₂SO₂CClFCClF₂, CF₃CF₂SO₂CBrFCBrF₂, CF₃CF₂SO₂CFICF₃, CF₃CF₂SO₂CF₂CF₂I, (CF₃)₂CFSO₂CHF₂, (CF₃)₂CFSO₂CClF₂, (CF₃)₂CFSO₂CBrF₂, (CF₃)₂CFSO₂CF₂I, (CF₃)₂CFSO₂CHClCF₃, (CF₃)₂CFSO₂CHFCBrF₂, (CF₃)₂CFSO₂CCl₂CF₃, (CF₃)₂CFSO₂CClFCClF₂, (CF₃)₂CFSO₂CBrFCBrF₂, (CF₃)₂CFSO₂CFICF₃ and (CF₃)₂CFSO₂CF₂CF₂I.
 4. A perfluorosulfone selected from the group consisting of: CF₃SO₂CF₂CF₂CF₃, CF₃SO₂C(CF₃)₃, CF₃SO₂CF₂CF(CF₃)₂, CF₃SO₂CF(CF₃)CF₂CF₃, CF₃CF₂SO₂CF₂CF₂CF₃, CF₃CF₂SO₂CF(CF₃)₂, CF₃CF₂CF₂SO₂CF(CF₃)₂, and (CF₃)₂CFSO₂CF(CF₃)₂.
 5. A hydrofluorosulfone selected from the group consisting of: CF₃CH₂SO₂CF₂CF₃, CF₃CH₂SO₂CF(CF₃)₂ and CH₃SO₂CF₂CF₃.
 6. A halomethyl perfluoroalkylsulfone selected from the group consisting of: CH₂ClSO₂CF₂CF₃, CH₂BrSO₂CF₂CF₃, CH₂ISO₂CF₂CF₃, CH₂ClSO₂CF(CF₃)₂, CH₂BrSO₂CF(CF₃)₂, CH₂ISO₂CF(CF₃)₂, CH₂ClSO₂CF₂CF₂CF₃, CH₂BrSO₂CF₂CF₂CF₃, CH₂ISO₂CF₂CF₂CF₃, CH₂BrCH₂SO₂CF₃, CH₂ClCH₂SO₂C₂F₅ and CH₂BrCH₂SO₂C₂F₅.
 7. A compound of claim 3 which is CHF₂SO₂CF₂CF₃.
 8. A compound of claim 3 which is CHF₂SO₂CF(CF₃)₂.
 9. A compound of claim 3 which is CF₃SO₂CHF₂.
 10. A compound of claim 3 which is CF₃SO₂CClF₂.
 11. A compound of claim 3 which is CF₃SO₂CBrF₂.
 12. A compound of claim 3 which is CF₃SO₂CF₂I.
 13. A compound of claim 3 which is CF₃SO₂CHClCF₃.
 14. A compound of claim 3 which is CF₃SO₂CHFCBrF₂.
 15. A compound of claim 3 which is CF₃SO₂CClFCClF₂.
 16. A compound of claim 3 which is CF₃SO₂CBrFCBrF₂.
 17. A compound of claim 3 which is CF₃SO₂CFICF₃.
 18. A compound of claim 3 which is CF₃SO₂CF₂CF₂I.
 19. A compound of claim 3 which is CF₃CF₂SO₂CHF₂.
 20. A compound of claim 3 which is CF₃CF₂SO₂CClF₂.
 21. A compound of claim 3 which is CF₃CF₂SO₂CBrF₂.
 22. A compound of claim 3 which is CF₃CF₂SO₂CF₂I.
 23. A compound of claim 3 which is CF₃CF₂SO₂CHClCF₃.
 24. A compound of claim 3 which is CF₃CF₂SO₂CHFCBrF₂.
 25. A compound of claim 3 which is CF₃CF₂SO₂CCl₂CF₃.
 26. A compound of claim 3 which is CF₃CF₂SO₂CClFCClF₂.
 27. A compound of claim 3 which is CF₃CF₂SO₂CBrFCBrF₂.
 28. A compound of claim 3 which is CF₃CF₂SO₂CFICF₃.
 29. A compound of claim 3 which is CF₃CF₂SO₂CF₂CF₂I.
 30. A compound of claim 3 which is (CF₃)₂CFSO₂CHF₂.
 31. A compound of claim 3 which is (CF₃)₂CFSO₂CClF₂.
 32. A compound of claim 3 which is (CF₃)₂CFSO₂CBrF₂.
 33. A compound of claim 3 which is (CF₃)₂CFSO₂CF₂I.
 34. A compound of claim 3 which is (CF₃)₂CFSO₂CHClCF₃.
 35. A compound of claim 3 which is (CF₃)₂CFSO₂CHFCBrF₂.
 36. A compound of claim 3 which is (CF₃)₂CFSO₂CCl₂CF₃.
 37. A compound of claim 3 which is (CF₃)₂CFSO₂CClFCClF₂.
 38. A compound of claim 3 which is (CF₃)₂CFSO₂CBrFCBrF₂.
 39. A compound of claim 3 which is (CF₃)₂CFSO₂CFICF₃.
 40. A compound of claim 3 which is (CF₃)₂CFSO₂CF₂CF₂I.
 41. A compound of claim 4 which is CF₃SO₂CF₂CF₂CF₃.
 42. A compound of claim 4 which is CF₃SO₂C(CF₃)₃.
 43. A compound of claim 4 which is CF₃SO₂CF₂CF(CF₃)₂.
 44. A compound of claim 4 which is CF₃SO₂CF(CF₃)CF₂CF₃.
 45. A compound of claim 4 which is CF₃CF₂SO₂CF₂CF₂CF₃.
 46. A compound of claim 4 which is CF₃CF₂SO₂CF(CF₃)₂.
 47. A compound of claim 4 which is CF₃CF₂CF₂SO₂CF(CF₃)₂.
 48. A compound of claim 4 which is (CF₃)₂CFSO₂CF(CF₃)₂.
 49. A compound of claim 5 which is CF₃CH₂SO₂CF₂CF₃.
 50. A compound of claim 5 which is:CF₃CH₂SO₂CF(CF₃)₂.
 51. A compound of claim 5 which is:CH₃SO₂CF₂CF₃.
 52. A compound of claim 6 which is CH₂ClSO₂CF₂CF₃.
 53. A compound of claim 6 which is CH₂BrSO₂CF₂CF₃.
 54. A compound of claim 6 which is CH₂ISO₂CF₂CF₃.
 55. A compound of claim 6 which is CH₂ClSO₂CF(CF₃)₂.
 56. A compound of claim 6 which is CH₂BrSO₂CF(CF₃)₂.
 57. A compound of claim 6 which is CH₂ISO₂CF(CF₃)₂.
 58. A compound of claim 6 which is CH₂ClSO₂CF₂CF₂CF₃.
 59. A compound of claim 6 which is CH₂BrSO₂CF₂CF₂CF₃.
 60. A compound of claim 6 which is CH₂ISO₂CF₂CF₂CF₃.
 61. A compound of claim 6 which is CH₂BrCH₂SO₂CF₃.
 62. A compound of claim 6 which is CH₂ClCH₂SO₂C₂F₅.
 63. A compound of claim 6 which is CH₂BrCH₂SO₂C₂F₅. 